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Phloroglucinol derivatives of Dryopteris dickinsii and some related ferns
PHYTXHEMICALREPORTS
2881
Phytochemistry. 1972, Vol. 11,pp. 2881to 2882. PersamonPress. Printedin England.
FILICINAE ASPIDIACEAE PHLOROGLUCINOL S. Faculty of Pharmaceutical
DERIVATIVES OF DR YOPTEHS AND SOME RELATED FERNS HISADA, K. SHIRAISHI
Sciences, Nagoya
and I.
DICKlNsI
INAGAKI
City University,
Mizuho-ku,
Nagoya,
Japan
(Received 26 April 1912)
Key Word Index-Dryopteris
dickinsii; Aspidiaceae;
ferns; acylphloroglucinols;
norflavaspidic
acid AB.
In the previous paper’ we reported that three filixic acids BBB, ABB and ABA were isolated from Dryopteris dickinsii (Fr. et Sav.) C. Chr. Here, we report the isolation of a new constituent, norflavaspidic acid AB (I) from the rhizomes of this fern. The raw filicin obtained by MgO method was chromatographed on silica and eluted with cyclohexaneCHCl, (1: 1)’ then with CHCl, alone. CHCIJ elution afforded I, Cz1Hz408, m.p. 105-107”, m/e 404 (M+), significant peaks at m/e 208, 196, 165, 153. IR vgf; cm-l; 3200 (OH), 2900, 1640 (conjugated C=O), 1605 (conjugated C=C), 1233, 1193, 1147. UV hEzH nm (log c); 226.5 (4*34), 292.5 (4*31), 341 (4.07), UV XE,‘,O,HH+NaoH nm (log 6); 242.5 (4*41), 321 (4.37). The NMR spectrum (NMR analysis in CDC13 + D,O using TMS as internal reference showed ppm) of I shows signalattributable to: 1.01 (3H, t -COCH2CH,CH,), about 1.72 (2H, m -COCH,CH,CH& 3.16 (2H, t -COCH2CH,CHs) all due to butyryl group. 1.45 (weak), 1.53 (6H, each s gem-dimethyl), 2.77 (3H, s -COCHJ), 3.62 (2H, s methylene bridge between acetylfilicinic acid and phlorobutyrophenone), 6.03 (1H, s free H of aromatic ring). After alkaline cleavage of I, phloroglucinol, methylphloroglucinol, phlorobutyrophenone, methylphlorobutyrophenone, filicinic acid, and acetylfilicinic acid were identified by TLC comparisons with authentic samples. The structure of I was further confirmed by the following two chemical reactions.
R
= CH2CH2CH3
SCHEME1. REACTIONSOF NORFLAVASPIDIC ACID AB. PHYT0
1119-P
2882
PHM~CHEM~CALREPORTS
I and acetylfilicinic acid (II) in the presence of 3.7% formalin were reacted together in dilute alkaline solution to obtain albaspidin AA (III), CZ1Hz408, m.p. 170-173” and filixic acid ABA (IV), C32H360,2, m.p. 164-167”. In the next, I and excess dimedone (V) were reacted together in dilute alkaline solution to yield II, C10H1404, m.p. 170-173”, methylenebis-dimedone (VI), C1,Hz404, m.p. 189” and phlorobutyrophenone (VII), C10H1204, m.p. 184-187”. All reaction products (II, III, IV, VI and VII) were identical with authentic samples. TABLE 1. CONSTITUENTS OF SOMEDryopteris SPECIES Locality
Dryopteris spp. D. dickinsii
BBB
Toyama Kumamoto Mie Shiga Kumamoto Kumamoto Kumamoto
D. tasiroi D. commixta
Filixic acid ABB ABA
(f+)
(S)
(Z)
(T)
(Z) (+)
5 +
(f+)
(1)
::; (+)
Norflavaspidic acid AB G) -r + + =i:
+, Isolated; (+), TLC spot; TLC-Plate, Kieslgel H; Solvent system, CHC&MeOHHZ0 = 7: 3: 1 (lower); Colour reag., Diazotized benzidine.
We have also investigated the occurrence sources of D. dickinsii, and D. tasiroi Tagawa showed in Table 1.
of phloroglucinol derivatives in the several and D. comrnixta Tagawa. The results were
Acknowledgements-The authors thank Dr. Y. Noro, Faculty of Pharmacy, Meijo University for measurement of MS, Mr. S. Morikawa for measurement for NMR spectra and Mrs. T. Ban and Mrs. S. Ito for elemental analysis. 1 S. HISADA, K. SHIRAI~HIand I. INAGAKI,Phytochem. 11, 1850 (1972).
Phytochemistry,
1972, Vol. 11, pp. 2882 to 2883.
Pergamon
Press.
Printed in England.
DENNSTAEDTIACEAE STEROLS
AND
TRITERPENES
OF OLEANDRA
PISTILLARZS”
A. S. C. WAN School of Pharmacy,
University of Singapore, Singapore
and R. T. AEXEL and H. J. NICHOLAS Institute of Medical Education and Research and Department of Biochemistry, of Medicine, St. Louis, MO 63104, U.S.A.
St. Louis University School
(Received 25 April 1972) Key Word Index--Oleandra pistillaris; Dennstaedtiaceae;
sterols; triterpenes.
Plant. Oleandrapistillaris, Dennstaedtiaceae (Oleanroideae). Source. Cameron Highlands (Malaysia). Previous work. None. Present work. Ground plant material (whole plant; 660 g) extracted with hot EtOH * Part III in a series “Malaysian
Plants”. For part II see Phytochem. 11, 456 (1972).
2881
Phytochemistry. 1972, Vol. 11,pp. 2881to 2882. PersamonPress. Printedin England.
FILICINAE ASPIDIACEAE PHLOROGLUCINOL S. Faculty of Pharmaceutical
DERIVATIVES OF DR YOPTEHS AND SOME RELATED FERNS HISADA, K. SHIRAISHI
Sciences, Nagoya
and I.
DICKlNsI
INAGAKI
City University,
Mizuho-ku,
Nagoya,
Japan
(Received 26 April 1912)
Key Word Index-Dryopteris
dickinsii; Aspidiaceae;
ferns; acylphloroglucinols;
norflavaspidic
acid AB.
In the previous paper’ we reported that three filixic acids BBB, ABB and ABA were isolated from Dryopteris dickinsii (Fr. et Sav.) C. Chr. Here, we report the isolation of a new constituent, norflavaspidic acid AB (I) from the rhizomes of this fern. The raw filicin obtained by MgO method was chromatographed on silica and eluted with cyclohexaneCHCl, (1: 1)’ then with CHCl, alone. CHCIJ elution afforded I, Cz1Hz408, m.p. 105-107”, m/e 404 (M+), significant peaks at m/e 208, 196, 165, 153. IR vgf; cm-l; 3200 (OH), 2900, 1640 (conjugated C=O), 1605 (conjugated C=C), 1233, 1193, 1147. UV hEzH nm (log c); 226.5 (4*34), 292.5 (4*31), 341 (4.07), UV XE,‘,O,HH+NaoH nm (log 6); 242.5 (4*41), 321 (4.37). The NMR spectrum (NMR analysis in CDC13 + D,O using TMS as internal reference showed ppm) of I shows signalattributable to: 1.01 (3H, t -COCH2CH,CH,), about 1.72 (2H, m -COCH,CH,CH& 3.16 (2H, t -COCH2CH,CHs) all due to butyryl group. 1.45 (weak), 1.53 (6H, each s gem-dimethyl), 2.77 (3H, s -COCHJ), 3.62 (2H, s methylene bridge between acetylfilicinic acid and phlorobutyrophenone), 6.03 (1H, s free H of aromatic ring). After alkaline cleavage of I, phloroglucinol, methylphloroglucinol, phlorobutyrophenone, methylphlorobutyrophenone, filicinic acid, and acetylfilicinic acid were identified by TLC comparisons with authentic samples. The structure of I was further confirmed by the following two chemical reactions.
R
= CH2CH2CH3
SCHEME1. REACTIONSOF NORFLAVASPIDIC ACID AB. PHYT0
1119-P
2882
PHM~CHEM~CALREPORTS
I and acetylfilicinic acid (II) in the presence of 3.7% formalin were reacted together in dilute alkaline solution to obtain albaspidin AA (III), CZ1Hz408, m.p. 170-173” and filixic acid ABA (IV), C32H360,2, m.p. 164-167”. In the next, I and excess dimedone (V) were reacted together in dilute alkaline solution to yield II, C10H1404, m.p. 170-173”, methylenebis-dimedone (VI), C1,Hz404, m.p. 189” and phlorobutyrophenone (VII), C10H1204, m.p. 184-187”. All reaction products (II, III, IV, VI and VII) were identical with authentic samples. TABLE 1. CONSTITUENTS OF SOMEDryopteris SPECIES Locality
Dryopteris spp. D. dickinsii
BBB
Toyama Kumamoto Mie Shiga Kumamoto Kumamoto Kumamoto
D. tasiroi D. commixta
Filixic acid ABB ABA
(f+)
(S)
(Z)
(T)
(Z) (+)
5 +
(f+)
(1)
::; (+)
Norflavaspidic acid AB G) -r + + =i:
+, Isolated; (+), TLC spot; TLC-Plate, Kieslgel H; Solvent system, CHC&MeOHHZ0 = 7: 3: 1 (lower); Colour reag., Diazotized benzidine.
We have also investigated the occurrence sources of D. dickinsii, and D. tasiroi Tagawa showed in Table 1.
of phloroglucinol derivatives in the several and D. comrnixta Tagawa. The results were
Acknowledgements-The authors thank Dr. Y. Noro, Faculty of Pharmacy, Meijo University for measurement of MS, Mr. S. Morikawa for measurement for NMR spectra and Mrs. T. Ban and Mrs. S. Ito for elemental analysis. 1 S. HISADA, K. SHIRAI~HIand I. INAGAKI,Phytochem. 11, 1850 (1972).
Phytochemistry,
1972, Vol. 11, pp. 2882 to 2883.
Pergamon
Press.
Printed in England.
DENNSTAEDTIACEAE STEROLS
AND
TRITERPENES
OF OLEANDRA
PISTILLARZS”
A. S. C. WAN School of Pharmacy,
University of Singapore, Singapore
and R. T. AEXEL and H. J. NICHOLAS Institute of Medical Education and Research and Department of Biochemistry, of Medicine, St. Louis, MO 63104, U.S.A.
St. Louis University School
(Received 25 April 1972) Key Word Index--Oleandra pistillaris; Dennstaedtiaceae;
sterols; triterpenes.
Plant. Oleandrapistillaris, Dennstaedtiaceae (Oleanroideae). Source. Cameron Highlands (Malaysia). Previous work. None. Present work. Ground plant material (whole plant; 660 g) extracted with hot EtOH * Part III in a series “Malaysian
Plants”. For part II see Phytochem. 11, 456 (1972).